Note: Descriptions are shown in the official language in which they were submitted.
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
TOPICAL COMPOSITION COMPRISING
A DIAZONIUM SALT-BASED COSMETIC BONDING AGENT
This application claims the benefit of U.S. Provisional Application No.
60/273,931 filed
March 7, 2001.
FIELD OF INVENTION
The present invention relates to cosmetic compositions suitable for use on
mammalian
skin. These compositions comprise a bonding agent capable of attaching a
cosmetic benefit
agent to mammalian skin. In particular, the bonding agent is a diazonium salt
linked to the
cosmetic benefit agents that are then in turn linked directly or indirectly to
the skin.
BACKGROUND
It is well known in the skin beauty care field that cosmetic benefit agents
may be topically
applied to human skin. There are a number of benefit agents that can be
applied to the skin for
varying purposes including moisturizers, humectants, color cosmetics, etc.
There is, however, a
common problem that arises in each of these areas. The problem is the lack of
substantivity of
the cosmetic benefit agents to the skin to which they are applied. That is,
the benefit agents that
are applied fail to "stick" to the skin such that a longwear result is
achieved to any noticeable
extent.
The present invention seeks to solve this substantivity deficiency that is
typical in topically
applied products by utilizing a chemical hook based technology. The operative
chemical hook of
the present invention is a diazonium salt bonding agent that serves as a
gluing mechanism
between a cosmetic benefit agent of interest and one or more protein molecules
that are found in
the skin. In particular, Applicants have found that diazonium salts serve as
suitable bonding
agents such that improved substantivity of various benefit agents are observed
on the skin.
Without being limited by theory, the chemical hook bonding agents covalently
bond to
certain amino acids present in proteinaceous substrates like skin, cuticles,
and hair to form a
substantive attachment of the desired cosmetic benefit agent to the substrate
as demonstrated by
the chemical reaction that follows
N~NCI- / AA'-Protein
Protein-AA
wherein AA represents functional amino acids containing amino, sulfhydryl,
carboxyl, or hydroxyl
groups and X is defined below.
SUMMARY OF THE INVENTION
The present invention relates to cosmetic compositions that comprise: a) a
safe and
effective amount of a diazonium salt bonding agent having the structure
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
N+ NCI
X
wherein X represents a cosmetic benefit agent that may or may not be attached
to a chemical
linker; and b) a cosmetically acceptable carrier for the bonding agent wherein
the composition is
administered topically to mammalian proteinaceous substrates and wherein the
bonding agent
reacts with a protein contained in the substrate such that the bonding agent,
and thus the
cosmetic benefit agent, is covalently attached to the substrate. The invention
further relates to
methods of using the compositions described above as well as various products
that include the
claimed compositions.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to topical compositions capable of delivering
substantively
attached cosmetic benefit agents to mammalian skin. The essential components
of these
compositions are described below. Also included is a nonexclusive description
of various optional
and preferred components useful in embodiments of the present invention.
As used herein, "safe and effective amount" means an amount of a compound,
component, or composition (as applicable) sufficient to significantly induce a
positive effect (e.g.,
confer a noticeable cosmetic benefit), but low enough to avoid serious side
effects, (e.g., undue
toxicity or allergic reaction), i.e., to provide a reasonable benefit to risk
ratio, within the scope of
sound medical judgment.
As used herein, "cosmetic benefit agent" means a compound, material, and/or
active that
confers an aesthetic feature to the surface, preferably skin, to which it is
applied.
As used herein, "chemical linker" refers to a hydrocarbon chain, optionally
containing
heteroatoms, e.g., S, N, Se, O, substituted or unsubstituted aryls, Si, SiO,
siloxane "D" groups
[{(CH3)}-Si-03], siloxane "M" groups {(CH3)3}-Si-O], and siloxane "T" groups
[{(CH3)}-Si-03,~]that
form a covalent bond between the cosmetic benefit agent and the bonding agent
such that a
"chemical hook" is formed.
The present invention can comprise, consist of, or consist essentially of any
of the required
or optional ingredients and/or limitations described herein.
All percentages and ratios are calculated on a weight basis unless otherwise
indicated. All
percentages are calculated based upon the total composition unless otherwise
indicated.
All molar weights are weight average molecular weights and are given in units
of grams per
mole.
All ingredient levels are exclusive of solvents, by-products, or other
impurities that may be
present in commercially available sources, unless otherwise indicated.
All measurements made are at ambient room temperature, which is approximately
73°F,
unless otherwise designated.
2
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
All documents referred to herein, including patents, patent applications, and
printed
publications, are hereby incorporated by reference in their entirety in this
disclosure.
DIAZONIUM SALT BONDING AGENT
The compositions of the present invention comprise a diazonium salt bonding
agent
having the structure
N+ NCh
X
wherein X represents a cosmetic benefit agent that may or may not be attached
to a chemical
linker. In preferred embodiments, X may be attached to a chemical linker that
acts as a connector
between X and the diazonium salt bonding agent. Suitable chemical linkers
include, but are not
limited to, hydrocarbon chains containing heteroatoms like S, N, Se, O,
substituted or
unsubstituted aryls, Si, SiO, siloxane "D" groups [{(CH3)}-Si-03], siloxane
"M" groups {(CH3)3}-SI-
O], and siloxane "T" groups [{(CH3)}-Si-03,2], etc.. In even more preferred
embodiments, the
chemical linker is an aryl group. It has been found that an aryl linker
provides enhanced stability
of the bonding agent.
The cosmetic benefit agent of the present invention is suitable for providing
therapeutic or
aesthetic skin benefits by deposition and adhesion to skin. Suitable cosmetic
agents include, but
are not limited to those selected from the group consisting of absorbents,
anti-acne actives, anti-
caking agents, anti-cellulite agents, anti-foaming agents, anti-fungal
actives, anti-inflammatory
actives, anti-microbial actives, anti-oxidants, antiperspirant/deodorant
actives, anti-skin atrophy
actives, anti-viral agents, anti-wrinkle actives, artificial tanning agents
,and accelerators,
astringents, barrier repair agents, binders, buffering agents, bulking agents,
chelating agents,
colorants, dyes, enzymes, essential oils, film formers, flavors, fragrances,
humectants,
hydrocolloids, light diffusers, nail enamels, opacifying agents, optical
brighteners, optical
modifiers, particulates, perfumes, pH adjusters, sequestering agents, skin
conditioners/moisturizers, skin feel modifiers, skin protectants, skin
sensates, skin treating agents,
skin exfoliating agents, skin lightening agents, skin soothing and/or healing
agents, skin
thickeners, sunscreen actives, topical anesthetics, vitamin compounds, and
combinations thereof.
Cosmetic benefit agents of the present invention are substantially free of
antimicrobial polymers.
In particular, such agents are not intended include biguanide polymers. As
used herein,
"substantially free" means that the ingredient is included in such an amount
that is not readily
detectable by conventional methods.
Suitable colorants include those used in foundations, blushes, blemish
covering
compositions, and other typical color cosmetic products. Such agents, in
effect, result in
cosmetic composition that is suitable for make-up application.
3
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
The cosmetic benefit agents of the present invention are well suited and
capable of
attaching (either removably or fixably) to the bonding agent via the chemical
linker. In preferred
embodiments, the compositions of the present invention comprise from about
0.001 % to about
50%, by weight of the composition, of a combination of the bonding agent and
the cosmetic
benefit agent. In fact, even more preferred amounts of the combination in
increasing order of
preference are from about 0.01 % to about 35%, 0.1 % to about 20%, 0.1 % to
about 15%, 1 % to
about 10%, and 2% to about 7%, by weight of the composition. Furthermore, in
such
combinations it is preferred that the combination of the bonding agent and
cosmetic benefit agent
comprise from aboufi 10% to about 90%, by weight of the combination, of the
cosmetic benefit
agent. More preferably, the combination comprises from about 20% to about 90%,
of the
cosmetic benefit agent. Even more preferably, the combination comprises from
about 30% to
85%, of the cosmetic benefit agent. Still more preferably, the combination
comprises about 50%
of the cosmetic benefit agent. Suitable cosmetic benefit agents include but
are not limited to
those that follow.
Hydrophobic Conditioning Agents
The cosmetic benefit agent may be one or more hydrophobic conditioning agents.
Preferably, the weighted arithmetic mean solubility parameter of the
hydrophobic conditioning
agent is less than or equal to 10.5. It is recognized, based on this
mathematical definition of
solubility parameters, that it is possible, for example, to achieve the
required weighted arithmetic
mean solubility parameter, i.e., less than or equal to 10.5, for a hydrophobic
conditioning agent
comprising two or more compounds if one of the compounds has an individual
solubility
parameter greater than 10.5.
Solubility parameters are well known to the formulation chemist of ordinary
skill in the art
and are routinely used as a guide for determining compatibilities and
solubilities of materials in the
formulation process.
The solubility parameter of a chemical compound, b, is defined as the square
root of the
cohesive energy density for that compound. Typically, a solubility parameter
for a compound is
calculated from tabulated values of the additive group contributions for the
heat of vaporization
and molar volume of the components of that compound, using the following
equation:
1 /2
Tl
g
4
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
wherein Ei Ei = the sum of the heat of vaporization additive group
contributions, and
~ m = the sum of the molar volume additive group contributions
i i
Standard tabulations of heat of vaporization and molar volume additive group
contributions for a
wide variety of atoms and groups of atoms are collected in Barton, A.F.M.
Handbook of Solubility
Parameters, CRC Press, Chapter 6, Table 3, pp. 64-66 (1985. The above
solubility parameter
equation is described in Fedors, R.F., "A Method for Estimating Both the
Solubility Parameters
and Molar Volumes of Liquids", Polymer Enqineering and Science, vol. 14, no.
2, pp. 147-154
(February 1974).
Solubility parameters obey the law of mixtures such that the solubility
parameter for a
mixture of materials is given by the weighted arithmetic mean (i.e. the
weighted average) of the
solubility parameters for each component of that mixture. See, Handbook of
Chemistry and
Physics, 57th edition, CRC Press, p. C-726 (1976-1977.
Solubility parameters have also been tabulated for a wide variety of chemical
materials.
Tabulations of solubility parameters are found in the above-cited Handbook of
Solubility
Parameters. Also, see "Solubility Effects In Product, Package, Penetration,
And Preservation",
C.D. Vaughan, Cosmetics and Toiletries, vol. 103, October 1988, pp. 47-69.
Nonlimiting examples of hydrophobic conditioning agents include those selected
from the
group consisting of mineral oil, petrolatum, lecithin, hydrogenated lecithin,
lanolin, lanolin
derivatives, C7-C40 branched chain hydrocarbons, C1-C30 alcohol esters of C1-
C30 carboxylic
acids, C1-C30 alcohol esters of C2-C30 dicarboxylic acids, monoglycerides of
C1-C30 carboxylic
acids, diglycerides of C1-C30 carboxylic acids, triglycerides of C1-C30
carboxylic acids, ethylene
glycol monoesters of C1-C30 carboxylic acids, ethylene glycol diesters of C1-
C30 carboxylic
acids, propylene glycol monoesters of C1-C30 carboxylic acids, propylene
glycol diesters of C1-
C30 carboxylic acids, C1-C30 carboxylic acid monoesters and polyesters of
sugars,
polydialkylsiloxanes, polydiarylsiloxanes, polyalkarylsiloxanes,
cylcomethicones having 3 to 9
silicon atoms, vegetable oils, hydrogenated vegetable oils, polypropylene
glycol C4-C20 alkyl
ethers, di C8-C30 alkyl ethers, and combinations thereof.
Straight and branched chain hydrocarbons having from about 7 to about 40
carbon atoms
are useful herein. Nonlimiting examples of these hydrocarbon materials include
dodecane,
isododecane, squalane, cholesterol, hydrogenated polyisobutylene, docosane
(i.e. a C22
hydrocarbon), hexadecane, isohexadecane (a commercially available hydrocarbon
sold as
Permethyl~ 101A by Presperse, South Plainfield, NJ). C7-C40 isoparaffins, a
class of C7-C40
branched hydrocarbons, are useful herein. Polydecene, a branched liquid
hydrocarbon, is also
useful herein and is commercially available under the tradenames Puresyn 100~
and Puresyn
3000~ from Mobile Chemical (Edison, NJ).
5
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
Also useful are C1-C30 alcohol esters of C1-C30 carboxylic acids and of C2-C30
dicarboxylic acids, including straight and branched chain materials as well as
aromatic
derivatives. Also useful are esters such as monoglycerides of C1-C30
carboxylic acids,
diglycerides of C1-C30 carboxylic acids, triglycerides of C1-C30 carboxylic
acids, ethylene glycol
monoesters of C1-C30 carboxylic acids, ethylene glycol diesters of C1-C30
carboxylic acids,
propylene glycol monoesters of C1-C30 carboxylic acids, and propylene glycol
diesters of C1-C30
carboxylic acids. Straight chain, branched chain and aryl carboxylic acids are
included herein.
Also useful are propoxylated and ethoxylated derivatives of these materials.
Nonlimiting
examples include diisopropyl sebacate, diisopropyl adipate, isopropyl
myristate, isopropyl
palmitate, myristyl propionate, ethylene glycol distearate, 2-ethylhexyl
palmitafe, isodecyl
neopentanoate, di-2-ethylhexyl maleate, cetyl palmitate, myristyl myristate,
stearyl stearate, cetyl
stearate, behenyl behenrate, dioctyl maleate, dioctyl sebacate, diisopropyl
adipate, cetyl
octanoate, diisopropyl dilinoleate, carpylic/capric triglyceride, PEG-6
caprylic/capric triglyceride,
PEG-8 caprylic/capric triglyceride, and combinations thereof.
Also useful are various C1-C30 monoesters and polyesters of sugars and related
materials. These esters are derived from a sugar or polyol moiety and one or
more carboxylic
acid moieties. Depending on the constituent acid and sugar, these esters can
be in either liquid
or solid form at room temperature. Examples of liquid esters include: glucose
tetraoleate, the
glucose tetraesters of soybean oil fatty acids (unsaturated), the mannose
tetraesters of mixed
soybean oil fatty acids, the galactose tetraesters of oleic acid, the
arabinose tetraesters of linoleic
acid, xylose tetralinoleate, galactose pentaoleate, sorbitol tetraoleate, the
sorbitol hexaesters of
unsaturated soybean oil fatty acids, xylitol pentaoleate, sucrose tetraoleate,
sucrose pentaoletate,
sucrose hexaoleate, sucrose hepatoleate, sucrose octaoleate, and mixtures
thereof. Examples of
solid esters include: sorbitol hexaester in which the carboxylic acid ester
moieties are palmitoleate
and arachidate in a 1:2 molar ratio; the octaester of raffinose in which the
carboxylic acid ester
moieties are linoleate and behenate in a 1:3 molar ratio; the heptaester of
maltose wherein the
esterifying carboxylic acid moieties are sunflower seed oil fatty acids and
lignocerate in a 3:4
molar ratio; the octaester of sucrose wherein the esterifying carboxylic acid
moieties are oleate
and behenate in a 2:6 molar ratio; and the octaester of sucrose wherein the
esterifying carboxylic
acid moieties are laurate, linoleate and behenate in a 1:3:4 molar ratio. A
preferred solid material
is sucrose polyester in which the degree of esterification is 7-8, and in
which the fatty acid
moieties are C18 mono- and/or di-unsaturated and behenic, in a molar ratio of
unsaturates:
~behenic of 1:7 to 3:5. A particularly preferred solid sugar polyester is the
octaester of sucrose in
which there are about 7 behenic fatty acid moieties and about 1 oleic acid
moiety in the molecule.
Other materials include cottonseed oil or soybean oil fatty acid esters of
sucrose. The ester
materials are further described in, U. S. Patent No. 2,831,854, U. S. Patent
No. 4,005,196, to
Jandacek, issued January 25, 1977; U. S. Patent No. 4,005,195, to Jandacek,
issued January 25,
6
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
1977, U. S. Patent No. 5,306,516, to Letton et al., issued April 26, 1994; U.
S. Patent No.
5,306,515, to Letton et al., issued April 26, 1994; U. S. Patent No.
5,305,594, to Letton et al.,
issued April 26, 1994; U. S. Patent No. 4,797,300, to Jandacek et al., issued
January 10, 1989; U.
S. Patent No. 3,963,699, to Rizzi et al, issued June 15, 1976; U. S. Patent
No. 4,518,772, to
Volpenhein, issued May 21, 1985; and U. S. Patent No. 4,517,360, to
Volpenhein, issued May 21,
1985.
Nonvolatile silicones such as polydialkylsiloxanes, polydiarylsiloxanes, and
polyalkarylsiloxanes are also useful oils. These silicones are disclosed in U.
S. Patent No.
5,069,897, to Orr, issued December 3, 1991. The polyalkylsiloxanes correspond
to the general
chemical formula R3Si0[R2Si0]xSiR3 wherein R is an alkyl group (preferably R
is methyl or ethyl,
more preferably methyl) and x is an integer up to about 500, chosen to achieve
the desired
molecular weight. Commercially available polyalkylsiloxanes include the
polydimethylsiloxanes,
which are also known as dimethicones, nonlimiting examples of which include
the Vicasil~ series
sold by General Electric Company and the Dow Corning 200 series sold by Dow
Corning
95 Corporation. Specific examples of polydimethylsiloxanes useful herein
include Dow Corning~
225 fluid having a viscosity of 10 centistokes and a boiling point greater
than 200°C, and Dow
Corning 200 fluids having viscosities of 50, 350, and 12,500 centistokes,
respectively, and
boiling points greater than 200°C. Also useful are materials such as
trimethylsiloxysilicate, which
is a polymeric material corresponding to the general chemical formula
[(CH2)3Si01~2]x[SiO2]y,
wherein x is an integer from about 1 to about 500 and y is an integer from
about 1 to about 500.
A commercially available trimethylsiloxysilicate is sold as a mixture with
dimethicone as Dow
Corning 593 fluid. Also useful herein are dimethiconols, which are hydroxy
terminated dimethyl
silicones. These materials can be represented by the general chemical formulas
R3Si0[R2Si0]xSiR20H and HOR2Si0[R2Si0]xSiR20H wherein R is an alkyl group
(preferably R
is methyl or ethyl, more preferably methyl) and x is an integer up to about
500, chosen to achieve
the desired molecular weight. Commercially available dimethiconols are
typically sold as mixtures
with dimethicone or cyclomethicone (e.g. Dow Corning~ 1401, 1402, and 1403
fluids). Also
useful herein are polyalkylaryl siloxanes, with polymethylphenyl siloxanes
having viscosities from
about 15 to about 65 centistokes at 25°C being preferred. These
materials are available, for
example, as SF 1075 methylphenyl fluid (sold by General Electric Company) and
556 Cosmetic
Grade phenyl trimethicone fluid (sold by Dow Corning Corporation). Alkylated
silicones such as
methyldecyl silicone and methyloctyl silicone are useful herein and are
commercially available
from General Electric Company. Also useful herein are alkyl modified siloxanes
such as alkyl
methicones and alkyl dimethicones wherein the alkyl chain contains 10 to 50
carbons. Such
siloxanes are commercially available under the tradenames ABIL WAX 9810 (C24-
Ca8 alkyl
methicone) (sold by Goldschmidt) and SF1632 (cetearyl methicone)(sold by
General Electric
7
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
Company). Cyclomethicone/dimethicone copolyol mixtures are also particularly
useful as
formulation aid/conditioning agents. A suitable mixture is sold under the
tradename DC 3225Q~.
Vegetable oils and hydrogenated vegetable oils are also useful herein.
Examples of
vegetable oils and hydrogenated vegetable oils include safflower oil, castor
oil, coconut oil,
cottonseed oil, menhaden oil, palm kernel oil, palm oil, peanut oil, soybean
oil, rapeseed oil,
linseed oil, rice bran oil, pine oil, sesame oil, sunflower seed oil,
hydrogenated safflower oil,
hydrogenated castor oil, hydrogenated coconut oil, hydrogenated cottonseed
oil, hydrogenated
menhaden oil, hydrogenated palm kernel oil, hydrogenated palm oil,
hydrogenated peanut oil,
hydrogenated soybean oil, hydrogenated rapeseed oil, hydrogenated linseed oil,
hydrogenated
rice bran oil, hydrogenated sesame oil, hydrogenated sunflower seed oil, and
mixtures thereof.
Also useful are C4-C20 alkyl ethers of polypropylene glycols, C1-C20
carboxylic acid
esters of polypropylene glycols, and di-C8-C30 alkyl ethers. Nonlimiting
examples of these
materials include PPG-14 butyl ether, PPG-15 stearyl ether, dioctyl ether,
dodecyl octyl ether, and
mixtures thereof.
Hydrophobic chelating agents are also useful herein as hydrophobic
conditioning agents.
Suitable agents are described in U. S. Patent No. 4,387,244, issued to Scanlon
et al. on June 7,
1983, and copending U. S. Patent Application Serial Nos. 09/258,747 and
09/259,485, filed in the
names of Schwartz et al. on February 26, 1999.
Preferred hydrophobic conditioning agents are selected from the group
consisting of
mineral oil, petrolatum, lecithin, hydrogenated lecithin, lanolin, lanolin
derivatives, C7-C40
branched chain hydrocarbons, C1-C30 alcohol esters of C1-C30 carboxylic acids,
C1-C30 alcohol
esters of C2-C30 dicarboxylic acids, monoglycerides of C1-C30 carboxylic
acids, diglycerides of
C1-C30 carboxylic acids, triglycerides of C1-C30 carboxylic acids, ethylene
glycol monoesters of
C1-C30 carboxylic acids, ethylene glycol diesters of C1-C30 carboxylic acids,
propylene glycol
monoesters of C1-C30 carboxylic acids, propylene glycol diesters of C1-C30
carboxylic acids, C1-
C30 carboxylic acid monoesters and polyesters of sugars, polydialkylsiloxanes,
polydiarylsiloxanes, polyalkylarylsiloxanes, cylcomethicones having 3 to 9
silicon atoms,
vegetable oils, hydrogenated vegetable oils, polypropylene glycol C4-C20 alkyl
ethers, di C8-C30
alkyl ethers, and combinations thereof.
Hydrophilic Conditioning Agents
The cosmetic benefit agents of the present invention can also be one or more
hydrophilic
conditioning agents. Nonlimiting examples of hydrophilic conditioning agents
include those
selected from the group consisting of polyhydric alcohols, polypropylene
glycols, polyethylene
glycols, ureas, pyrolidone carboxylic acids, ethoxylated and/or propoxylated
C3-C6 diols and
triols, alpha-hydroxy C2-C6 carboxylic acids, ethoxylated and/or propoxylated
sugars, polyacrylic
acid copolymers, sugars having up to about 12 carbons atoms, sugar alcohols
having up to about
12 carbon atoms, and mixtures thereof. Specific examples of useful hydrophilic
conditioning
8
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
agents include materials such as urea; guanidine; glycolic acid and glycolate
salts (e.g.,
ammonium and quaternary alkyl ammonium); lactic acid and lactate salts (e.g.,
ammonium and
quaternary alkyl ammonium); sucrose, fructose, glucose, eruthrose, erythritol,
sorbitol, mannitol,
glycerol, hexanetriol, propylene glycol, butylene glycol, hexylene glycol, and
the like; polyethylene
glycols such as PEG-2, PEG-3, PEG-30, PEG-50, polypropylene glycols such as
PPG-9, PPG-12,
PPG-15, PPG-17, PPG-20, PPG-26, PPG-30, PPG-34; alkoxylated glucose;
hyaluronic acid;
cationic skin conditioning polymers (e.g., quaternary ammonium polymers such
as
Polyquaternium polymers); and mixtures thereof. Glycerol, in particular, is a
preferred hydrophilic
conditioning agent in the articles of the present invention. Also useful are
materials such as aloe
vera in any of its variety of forms (e.g., aloe vera gel), chitosan and
chitosan derivatives, e.g.,
chitosan lactate, lactamide monoethanolamine; acetamide monoethanolamine; and
mixtures
thereof. Also useful are propoxylated glycerols as described in propoxylated
glycerols described
in U. S. Patent No. 4,976,953, to Orr et al., issued December 11, 1990.
Structured Conditioning Aqents
The cosmetic benefit agents of the present invention may also be structured
conditioning
agents. Suitable structured conditioning agents include, but are not limited
to, vesicular structures
such as ceramides, liposomes, and the like.
Coacervates
The cosmetic benefit agents of the present invention can be coacervate-
forming.
Preferably, the coacervate-forming cosmetic benefit agent comprises a cationic
polymer, an
anionic surfactant, and a dermatologically acceptable carrier for the polymer
and surfactant. The
cationic polymer may be selected from the group consisting of natural backbone
quaternary
ammonium polymers, synthetic backbone quaternary ammonium polymers, natural
backbone
amphoteric type polymers, synthetic backbone amphoteric type polymers, and
combinations
thereof.
More preferably, the cationic polymer is selected from the group consisting of
natural
backbone quaternary ammonium polymers selected from the group consisting of
Polyquaternium-
4, Polyquaternium-10, Polyquaternium-24, PG-hydroxyethylcellulose
alkyldimonium chlorides,
guar hydroxypropyltrimonium chloride, hydroxypropylguar hydroxypropyltrimonium
chloride, and
combinations thereof; synthetic backbone quaternary ammonium polymers selected
from the
group consisting of Polyquaternium-2, Polyquaternium-6, Polyquaternium-7,
Polyquaternium-11,
Polyquaternium-16, Polyquaternium-17, Polyquaternium-18, Polyquaternium-28,
Polyquaternium-
32, Polyquaternium-37, Polyquaternium-43, Polyquaternium-44, Polyquaternium-
46,
polymethacylamidopropyl trimonium chloride, acrylamidopropyl trimonium
chloride/acrylamide
copolymer, and combinations thereof; natural backbone amphoteric type polymers
selected from
the group consisting of chitosan, quaternized proteins, hydrolyzed proteins,
and combinations
thereof; synthetic backbone amphoteric type polymers selected from the group
consisting of
9
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
Polyquaternium-22, Polyquaternium-39, Polyquaternium-47, adipic
acid/dimethylaminohydroxypropyl diethylenetriamine copolymer,
polyvinylpyrrolidone/dimethylyaminoethyl methacyrlate copolymer,
vinylcaprolactam/
polyvinylpyrrolidone/dimethylaminoethylmethacrylate copolymer,
vinaylcaprolactam/
polyvinylpyrrolidone/dimethylaminopropylmethacrylamide terpolymer,
polyvinylpyrrolidone/dimethylaminopropylmethacrylamide copolymer, polyamine,
and
combinations thereof; and combinations thereof. Even more preferably, the
cationic polymer is a
synthetic backbone amphoteric type polymer. Even still more preferably, the
cationic polymer is a
polyamine.
When the cationic polymer is a polyamine, it is preferred that the cationic
polyamine
polymer be selected from the group consisting of polyethyleneimines,
polyvinylamines,
polypropyleneimines, polylysines and combinations thereof. Even more
preferably, the cationic
polyamine polymer is a polyethyleneimine.
In certain embodiments in which the cationic polymer is a polyamine, the
polyamine may
be hydrophobically or hydrophilically modified. In this instance, the cationic
polyamine polymer is
selected from the group consisting of benzylated polyamines, ethoxylated
polyamines,
propoxylated polyamines, alkylated polyamines, amidated polyamines, esterified
polyamines and
combinations thereof. The composition comprises from about 0.01 % to about
20%, more
preferably from about 0.05% to about 10%, and most preferably from about 0.1 %
to about 5%, by
weight of the composition, of the cationic polymer.
Preferably, for the coacervate-forming cosmetic benefit agent, the anionic
surfactant is
selected from the group consisting of sarcosinates, glutamates, sodium alkyl
sulfates, ammonium
alkyl sulfates, sodium alkyleth sulfates, ammonium alkyleth sulfates, ammonium
laureth-n-
sulfates, sodium laureth-n-sulfates, isethionates, glycerylether sulfonates,
sulfosuccinates and
combinations thereof. More preferably, the anionic surfactant is selected from
the group
consisting of sodium lauroyl sarcosinate, monosodium lauroyl glutamate, sodium
alkyl sulfates,
ammonium alkyl sulfates, sodium alkyleth sulfates, ammonium alkyleth sulfates,
and
combinations thereof.
Suitable coacervate-forming agents are further described in copending U. S.
patent
applications Serial Nos. 09/397,747, filed in the name of Schwartz et al.;
09/397,746, filed in the
name of Heinrich et al.; 09/397,712, filed in the name of Schwartz et al.;
09/397,723, filed in the
name of Heinrich et al.; and 09/397,722, filed in the name of Venkitaraman et
al.; each of which
were filed on September 16, 1999.
Alternatively, the coacenrate-forming cosmetic benefit agent may comprise an
anionic
polymer, a cationic surfactant, and a dermatologically acceptable carrier for
the polymer and
surfactant. The anionic polymer may be selected from the group consisting of
polyacrylic acid
polymers, polyacrylamide polymers, copolymers of acrylic acid, acrylamide, and
other natural or
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
synthetic polymers (e.g., polystyrene, polybutene, polyurethane, etc.),
naturally derived gums, and
combinations thereof. Suitable gums include alginates (e.g., propylene glycol
alginate), pectins,
chitosans (e.g., chitosan lactate), and modified gums (e.g., starch octenyl
succinate), and
combinations thereof. More preferably, the anionic polymer is selected from
the group
consisting of polyacrylic acid polymers, polyacrylamide polymers, pectins,
chitosans, and
combinations thereof. Suitable cationic surfactants include, but are not
limited to, those
discussed herein.
Colorants
The present compositions may comprise a bonding agent that comprises one or
more
colorants. Suitable colorants include, but are not limited to, pigments, dyes
or lakes or a
combination thereof as the cosmetic benefit agents. Preferred pigments
include, but are not
limited to, iron oxides, and titanium oxides. Suitable dyes include FD&C
approved colorants, D&C
approved colorants, and those approved for use in Europe and Japan. See,
Marmion, D. M.,
Handbook of US Colorants for Food. Drugs, Cosmetics, and Medical Devices, 3rd
ed, 1991.
Vitamin Compounds
The present compositions may comprise vitamin compounds, precursors, and
derivatives
thereof as the cosmetic benefit agents. These vitamin compounds may be in
either natural or
synthetic form. Suitable vitamin compounds include, but are not limited to,
Vitamin A (e.g., beta
carotene, retinoic acid, retinol, retinoids, retinyl palmitate, retinyl
proprionate, etc.), Vitamin B
(e.g., niacin, niacinamide, riboflavin, pantothenic acid, etc.), Vitamin C
(e.g., ascorbic acid, etc.),
Vitamin D (e.g., ergosterol, ergocalciferol, cholecalciferol, etc.), Vitamin E
(e.g., tocopherol
acetate, etc.), and Vitamin IC (e.g., phytonadione, menadione, phthiocol,
etc.) compounds.
For instance, vitamin B3 compounds are particularly useful for regulating skin
condition as
described in co-pending U. S. Application Serial No. 08/834,010, filed April
11, 1997
(corresponding to international publication WO 97/39733 A1, published October
30, 1997) which
is incorporated by reference herein in its entirety. The compositions of the
present invention
preferably comprise from about 0.01 % to about 50%, more preferably from about
0.1 % to about
10%, even more preferably from about 0.5% to about 10%, and still more
preferably from about
1 % to about 5%, most preferably from about 2% to about 5%, of the vitamin B3
compound.
As used herein, "vitamin B3 compound" means a compound having the formula:
~R
wherein R is - CONH2 (i.e., niacinamide), - COOH (i.e., nicotinic acid) or -
CH20H (i.e., nicotinyl
alcohol); derivatives thereof; and salts of any of the foregoing.
11
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
Exemplary derivatives of the foregoing vitamin B3 compounds include nicotinic
acid
esters, including non-vasodilating esters of nicotinic acid, nicotinyl amino
acids, nicotinyl alcohol
esters of carboxylic acids, nicotinic acid N-oxide and niacinamide N-oxide.
Examples of suitable vitamin B3 compounds are well known in the art and are
commercially available from a number of sources, e.g., the Sigma Chemical
Company (St. Louis,
MO); ICN Biomedicals, Inc. (/ruin, CA) and Aldrich Chemical Company
(Milwaukee, WI).
The vitamin compounds may be included as the substantially pure material, or
as an
extract obtained by suitable physical and/or chemical isolation from natural
(e.g., plant) sources.
Anti-Acne Actives
Examples of useful anti-acne actives as the cosmetic benefit agents of the
present
invention include, but are not limited to, the keratolytics such as salicylic
acid (o-hydroxybenzoic
acid), derivatives of salicylic acid such as 5-octanoyl salicylic acid, and
resorcinol; retinoids such
as retinoic acid and its derivatives (e.g., cis and trans); sulfur-containing
D and L amino acids and
their derivatives and salts, particularly their N-acetyl derivatives, a
preferred example of which is
N-acetyl-L-cysteine; lipoic acid; antibiotics and antimicrobials such as
benzoyl peroxide, octopirox,
tetracycline, 2,4,4'-trichloro-2'-hydroxy diphenyl ether, 3,4,4'-
trichlorobanilide, azelaic acid and its
derivatives, phenoxyethanol, phenoxypropanol, phenoxyisopropanol, ethyl
acetate, clindamycin
and meclocycline; sebostats such as flavonoids; and bile salts such as scymnol
sulfate and its
derivatives, deoxycholate, and cholate.
Anti-Wrinkle and Anti-Skin Atrophy Actives
Examples of anti-wrinkle and anti-skin atrophy actives useful as the cosmetic
benefit
agents of the present invention include, but are not limited to, retinoic acid
and its derivatives
(e.g., cis and trans); retinol; retinyl esters; niacinamide, and derivatives
thereof; sulfur-containing
D and L amino acids and their derivatives and salts, particularly the N-acetyl
derivatives, a
preferred example of which is N-acetyl-L-cysteine; thiofs, e.g., ethane thiol;
terpene alcohols (e.g.,
farnesol); hydroxy acids, phytic acid, lipoic acid; lysophosphatidic acid,
alpha-hydroxy acids (e.g.,
lactic acid and glycolic acid), beta-hydroxy acids (e.g., salicylic acid), and
skin peel agents (e.g.,
phenol and the like).
Enzymes
The cosmetic benefit agents of the present invention may be one or more
enzymes.
Preferably, such enzymes are dermatologically acceptable. Suitable enzymes
include, but are
not limited to, keratinase, protease, amylase, subtilisin, other peptides and
proteins, etc..
Peptides, including but not limited to, di-, tri-, tetra-, and pentapeptides
and derivatives
thereof, may be included as the cosmetic benefit agents of the present
invention in amounts that
are safe and effective. As used herein, "peptides" refers to both the
naturally occuring peptides
and synthesized peptides. Also useful herein are naturally occurring and
commercially available
compositions that contain peptides.
12
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
Sunscreen Actives
Also useful herein as cosmetic benefit agents are sunscreening actives. A wide
variety of
sunscreening agents are described in U.S. Patent No. 5,087,445, to Haffey et
al., issued February
11, 1992; U.S. Patent No. 5,073,372, to Turner et al., issued December 17,
1991; U.S. Patent No.
5,073,371, to Turner et al. issued December 17, 1991; and Sagarin, et al., at
Chapter VIII, pages
189 et seq., of Cosmetics Science and Technoloay. Nonlimiting examples of
sunscreens which
are useful in the compositions of the present invention are those selected
from the group
consisting of 2-ethylhexyl p-methoxycinnamate, 2-ethylhexyl N,N-dimethyl-p-
aminobenzoate, p-
aminobenzoic acid, 2-phenylbenzimidazole-5-sulfonic acid, octocrylene,
oxybenzone,
homomenthyl salicylate, octyl salicylate, 4,4'-methoxy-t-
butyldibenzoylmethane, 4-isopropyl
dibenzoylmethane, 3-benzylidene camphor, 3-(4-methylbenzylidene) camphor,
titanium dioxide,
zinc oxide, silica, iron oxide, and mixtures thereof. Still other useful
sunscreens are those
disclosed in U.S. Patent No. 4,937,370, to Sabatelli, issued June 26, 1990;
and U.S. Patent No.
4,999,186, to Sabatelli et al., issued March 12, 1991. Especially preferred
examples of these
sunscreens include those selected from the group consisting of 4-N,N-(2-
ethylhexyl)methylaminobenzoic acid ester of 2,4-dihydroxybenzophenone, 4-N,N-
(2-
ethylhexyl)methylaminobenzoic acid ester with 4-hydroxydibenzoylmethane, 4-N,N-
(2-
ethylhexyl)-methylaminobenzoic acid ester of 2-hydroxy-4-(2-
hydroxyethoxy)benzophenone, 4-
N,N-(2-ethylhexyl)-methylaminobenzoic acid ester of 4-(2-
hydroxyethoxy)dibenzoylmethane, and
mixtures thereof. Exact amounts of sunscreens which can be employed will vary
depending upon
the sunscreen chosen and the desired Sun Protection Factor (SPF) to be
achieved. SPF is a
commonly used measure of photoprotection of a sunscreen against erythema.
Chelators
The bonding agents of the present compositions may also include chelators as
the
cosmetic benefit agent. As used herein, "chelator" or "chelating agent" means
an active agent
capable of removing a metal ion from a system by forming a complex so that the
metal ion cannot
readily participate in or catalyze chemical reactions. The inclusion of a
chelating agent is
especially useful for providing protection against UV radiation that can
contribute to excessive
scaling or skin texture changes and against other environmental agents, which
can cause skin
damage.
A safe and effective amount of a chelating agent may be added to the
compositions of the
subject invention, preferably in amounts of from about 0.1 % to about 10%,
more preferably from
about 1 % to about 5%, by weight of the composition. Exemplary chelators that
are useful herein
are disclosed in U.S. Patent No. 5,487,884, issued 1/30/96 to Bissett et al.;
International
Publication No. 91/16035, Bush et al., published 10/31/95; and International
Publication No.
91/16034, Bush et al., published 10/31/95. Preferred chelators useful in
compositions of the
13
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
subject invention are furildioxime, furildioxime derivatives, furilmonoxime,
furilmonoxime
derivatives, and combinations thereof.
Flavonoids
The cosmetic benefit agents of the present invention may also be a flavonoid
compound.
Flavonoids are broadly disclosed in U.S. Patents 5,686,082 and 5,686,367.
Flavonoids suitable
for use in the present invention are flavanones selected from the group
consisting of
unsubstituted flavanones, mono-substituted flavanones, and mixtures thereof;
chalcones selected
from the group consisting of unsubstituted chalcones, mono-substituted
chalcones, di-substituted
chalcones, tri-substituted chalcones, and mixtures thereof; flavones selected
from the group
consisting of unsubstituted flavones, mono-substituted flavones, di-
substituted flavones, and
mixtures thereof; one or more isoflavones; coumarins selected from the group
consisting of
unsubstituted coumarins, mono-substituted coumarins, di-substituted coumarins,
and mixtures
thereof; chromones selected from the group consisting of unsubstituted
chromones, mono-
substituted chromones, di-substituted chromones, and mixtures thereof; one or
more dicoumarols;
one or more chromanones; one or more chromanols; isomers (e.g., cis/trans
isomers) thereof;
and mixtures thereof. By the term "substituted" as used herein means
flavonoids wherein one or
more hydrogen atom of the flavonoid has been independently replaced with
hydroxyl, C1-C8
alkyl, C1-C4 alkoxyl, O-glycoside, and the like or a mixture of these
substituents.
Examples of suitable flavonoids include, but are not limited to, unsubstituted
flavanone,
mono-hydroxy flavanones (e.g., 2'-hydroxy flavanone, 6-hydroxy flavanone, 7-
hydroxy flavanone,
etc.), mono-alkoxy flavanones (e.g., 5-methoxy flavanone, 6-methoxy flavanone,
7-methoxy
flavanone, 4'-methoxy flavanone, etc.), unsubstituted chalcone (especially
unsubstituted trans
chalcone), mono-hydroxy chalcones (e.g., 2'-hydroxy ~chalcone, 4'-hydroxy
chalcone, etc.), di
hydroxy chalcones (e.g., 2', 4-dihydroxy chalcone, 2',4'-dihydroxy chalcone,
2,2'-dihydroxy
chalcone, 2',3-dihydroxy chalcone, 2',5'-dihydroxy chalcone, etc.), and tri-
hydroxy chalcones (e.g.,
2',3',4'-trihydroxy chalcone, 4,2',4'-trihydroxy chalcone, 2,2',4'-trihydroxy
chalcone, etc.),
unsubstituted flavone, 7,2'-dihydroxy flavone, 3',4'-dihydroxy naphthoflavone,
4'-hydroxy flavone,
5,6-benzoflavone, and 7,8-benzoflavone, unsubstituted isoflavone, daidzein
(7,4'-dihydroxy
isoflavone), 5,7-dihydroxy-4'-methoxy isoflavone, soy isoflavones (a mixture
extracted from soy),
unsubstituted coumarin, 4-hydroxy coumarin, 7-hydroxy coumarin, 6-hydroxy-4-
methyl coumarin,
unsubstituted chromone, 3-formyl chromone, 3-formyl-6-isopropyl chromone,
unsubstituted
dicoumarol, unsubstituted chromanone, unsubstituted chromanol, and mixtures
thereof.
Preferred for use herein are unsubstituted flavanone, methoxy flavanones,
unsubstituted
chalcone, 2', 4-dihydroxy chalcone, and mixtures thereof. Most preferred are
unsubstituted
flavanone, unsubstituted chalcone (especially the trans isomer), and mixtures
thereof.
They can be synthetic materials or obtained as extracts from natural sources
(e.g.,
plants). The naturally sourced material can also further be derivatized (e.g.,
a glycoside, an ester
14
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
or an ether derivative prepared following extraction from a natural source).
Flavonoid compounds
useful herein are commercially available from a number of sources, e.g.,
Indofine Chemical
Company, Inc. (Somerville, New Jersey), Steraloids, Inc. (Wilton, New
Hampshire), and Aldrich
Chemical Company, Inc. (Milwaukee, Wisconsin).
Mixtures of the above flavonoid compounds may also be used.
The herein described flavonoid compounds are preferably present in the instant
invention
at concentrations of from about 0.01 % to about 20%, more preferably from
about 0.1 % to about
10%, and most preferably from about 0.5% to about 5%.
Sterols
The cosmetic benefit agents of the present invention may also be a safe and
effective
amount of one or more sterol compounds. Examples of useful sterol compounds
include
sitosterol, stigmasterol, campesterol, brassicasterol, lanosterol, 7-
dehydrocholesterol, and
mixtures thereof. These can be synthetic in origin or from natural sources,
e.g., blends extracted
from plant sources (e.g., phytosterols).
Anti-Cellulite Agents
The cosmetic benefit agent may also be an anti-cellulite agent. Suitable
agents may
include, but are not limited to, xanthine compounds (e.g., caffeine,
theophylline, theobromine, and
aminophylline), forskolin, and derivatives thereof.
Skin Li hq teeing Agents
Another suitable cosmetic benefit agent is a skin lightening agent. When used,
the
compositions preferably comprise from about 0.1 % to about 10%, more
preferably from about
0.2% to about 5%, also preferably from about 0.5% to about 2%, by weight of
the composition, of
a skin lightening agent. Suitable skin lightening agents include those known
in the art, including
kojic acid, arbutin, deoxyarbutin, ascorbic acid and derivatives thereof,
e.g., magnesium ascorbyl
phosphate or sodium ascorbyl phosphate or other salts of ascorbyl phosphate.
COSMETICALLY ACCEPTABLE CARRIER
The compositions of the present invention comprise a cosmetically-acceptable
carrier or
vehicle for bonding agent and any optional components. Suitable carriers are
well known in the
art and are selected based on the end use application. For example, carriers
of the present
invention include, but are not limited to, those suitable for application to
skin. Preferably, the
carriers of the present invention are suitable for application to skin (e.g.,
sunscreens, creams,
milks, lotions, masks, serums, etc.) and nails (e.g., polishes, treatments,
etc.). Such carriers are
well-known to one of ordinary skill in the art, and can include one or more
compatible liquid or
solid filler diluents or vehicles which are suitable for application to skin
and nails. The exact
amount of carrier will depend upon the level of the bonding agent and any
other optional
ingredients that one of ordinary skill in the art would classify as distinct
from the carrier (e.g., other
active components). The compositions of the present invention preferably
comprise from about
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
75% to about 99.999%, more preferably from about 85% to about 99.99%, still
more preferably
from 90% to about 99%, and most preferably, from about 93% to about 98%, by
weight of the
composition, of a carrier.
The carrier and compositions herein can be formulated in a number of ways,
including but
not limited to emulsions (in emulsion technology, a composition comprising a
"dispersed phase"
and a "continuous phase;" the dispersed phase existing as small particles or
droplets that are
suspended in and surrounded by a continuous phase). For example, suitable
emulsions include
oil-in-water, water-in-oil, water-in-oil-in-water, oil-in-water-in-oil, and
oil-in-water-in-silicone
emulsions. Preferred compositions comprise an oil-in-water emulsion.
The compositions of the present invention can be formulated into a wide
variety of
product types, including creams, waxes, pastes, lotions, milks, mousses, gels,
oils, tonics, and
sprays. Preferred compositions are formulated into lotions, creams, gels, and
sprays. These
product forms may be used for a number of applications, including, but not
limited to, hand and
body lotions, cold creams, facial moisturizers, anti-acne preparations,
topical analgesics, make-
ups/cosmetics including foundations, eyeshadows, lipsticks, and the like. Any
additional
components required to formulate such products vary with product type and can
be routinely
chosen by one skilled in the art.
If compositions of the present invention are formulated as an aerosol and
applied to the
skin as a spray-on product, a propellant is added to the composition. Examples
of suitable
propellants include chlorofluorinated lower molecular weight hydrocarbons. A
more complete
disclosure of propellants useful herein can be found in Sagarin, Cosmetics
Science and
Technoloay, 2nd Edition, Vol. 2, pp. X43-465 (1972).
OPTIONAL INGREDIENTS
The compositions of the present invention may contain a variety of other
components
such as are conventionally used in a given product type provided that they do
not unacceptably
alter the benefits of the invention. These optional components should be
suitable for application
to mammalian skin, that is, when incorporated into the compositions they are
suitable for use in
contact with human skin without undue toxicity, incompatibility, instability,
allergic response, and
the ~like, within the scope of sound medical or formulator's judgment. The
CTFA Cosmetic
Ingredient Handbook, Second Edition (1992) describes a wide variety of
nonlimiting cosmetic and
pharmaceutical ingredients commonly used in the skin care industry, which are
suitable for use in
the compositions of the present invention. Examples of these ingredient
classes include:
enzymes, surfactants, abrasives, skin exfoliating agents, absorbents,
aesthetic components such
as fragrances, pigments, colorings/colorants, essential oils, skin sensates,
astringents, etc. (e.g.,
clove oil, menthol, camphor, eucalyptus oil, eugenol, menthyl lactate, witch
hazel distillate), anti-
acne agents (e.g., resorcinol, sulfur, salicylic acid, erythromycin, zinc,
etc.), anti-caking agents,
16
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
antifoaming agents, antimicrobial agents (e.g., iodopropyl butylcarbamate),
antioxidants, binders,
biological additives, buffering agents, bulking agents, chelating agents,
chemical additives,
colorants, cosmetic astringents, cosmetic biocides, denaturants, drug
astringents, external
analgesics, polymer beads, film formers or materials, e.g., polymers, for
aiding the film-forming
properties and substantivity of the composition (e.g., copolymer of eicosene
and vinyl
pyrrolidone), humectants, opacifying agents, pH adjusters, propellants,
reducing agents,
sequestrants, skin bleaching agents (or lightening agents) (e.g.,
hydroquinone, kojic acid,
ascorbic acid, magnesium ascorbyl phosphate, ascorbyl glucosamine), skin
soothing and/or
healing agents (e.g., panthenol and derivatives (e.g., ethyl panthenol), aloe
vera, pantothenic acid
and its derivatives, allantoin, bisabolol, and dipotassium glycyrrhizinate),
thickeners,
hydrocolloids, particular zeolites, and vitamins and derivatives thereof (e.g.
tocopherol, tocopherol
acetate, beta carotene, retinoic acid, retinol, retinoids, retinyl palmitate,
niacin, niacinamide, and
the like). The compositions of the present invention may include carrier
components such as are
known in the art. Such carriers can include one or more compatible liquid or
solid filler diluents or
vehicles that are suitable for application to skin.
The optional components useful herein can be categorized by their therapeutic
or
aesthetic benefit or their postulated mode of action. However, it is to be
understood that the
optional components useful herein can in some instances provide more than one
therapeutic or
aesthetic benefit or operate via more than one mode of action. Therefore,
classifications herein
are made for the sake of convenience and are not intended to limit the
component to that
particular application or applications listed. Also, when applicable, the
pharmaceutically-
acceptable salts of the components are useful herein.
Non-Steroidal Anti-Inflammatory Actives NSAIDS)
Examples of NSAIDS useful in the compositions of the present invention
include, but are
not limited to, the following categories: propionic acid derivatives; acetic
acid derivatives; fenamic
acid derivatives; biphenylcarboxylic acid derivatives; and oxicams. All of
these NSAIDS are fully
described in U. S. Patent 4,985,459 to Sunshine et al., issued January 15,
1991. Examples of
useful NSAIDS include acetyl salicylic acid, ibuprofen, naproxen,
benoxaprofen, flurbiprofen,
fenoprofen, fenbufen, ketoprofen, indoprofen, pirprofen, carprofen, oxaprozin,
pranoprofen,
miroprofen, tioxaprofen, suprofen, alminoprofen, tiaprofenic acid, fluprofen
and bucloxic acid.
Also useful are the steroidal anti-inflammatory drugs including hydrocortisone
and the like.
To~cal Anesthetics
Examples of topical anesthetic drugs suitable for inclusion in the
compositions of the
present invention include, but are not limited to, benzocaine, lidocaine,
bupivacaine,
chlorprocaine, dibucaine, etidocaine, mepivacaine, tetracaine, dyclonine,
hexylcaine, procaine,
cocaine, ketamine, pramoxine, phenol, and pharmaceutically acceptable salts
thereof.
17
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
Artificial Tanning Actives and Accelerators
Examples of artificial tanning actives and accelerators useful in the
compositions of the
present invention include, but are not limited to, dihydroxyacetaone,
tyrosine, tyrosine esters such
.as ethyl tyrosinate, and phospho-DOPA.
Antimicrobial and Antifungal Actives
Examples of antimicrobial and antifungal actives useful in the compositions of
the present
invention include, but are not limited to, 13-lactam drugs, quinolone drugs,
ciprofloxacin,
norfloxacin, tetracycline, erythromycin, amikacin, 2,4,4'-trichloro-2'-hydroxy
diphenyl ether, 3,4,4'-
trichlorocarbanilide, phenoxyethanol, phenoxy propanol, phenoxyisopropanol,
doxycycline,
capreomycin, chlorhexidine, chlortetracycline, oxytetracycline, clindamycin,
ethambutol,
hexamidine isethionate, metronidazole, pentamidine, gentamicin, kanamycin,
lineomycin,
methacycline, methenamine, minocycline, neomycin, netilmicin, paromomycin,
streptomycin,
tobramycin, miconazole, tetracycline hydrochloride, erythromycin, zinc
erythromycin, erythromycin
estolate, erythromycin stearate, amikacin sulfate, doxycycline hydrochloride,
capreomycin sulfate,
chlorhexidine gluconate, chlorhexidine hydrochloride, chlortetracycline
hydrochloride, oxytetra-
cycline hydrochloride, clindamycin hydrochloride, ethambutol hydrochloride,
metronidazole
hydrochloride, pentamidine hydrochloride, gentamicin sulfate, kanamycin
sulfate, lineomycin
hydrochloride, methacycline hydrochloride, methenamine hippurate, methenamine
mandelate,
minocycline hydrochloride, neomycin sulfate, netilmicin sulfate, paromomycin
sulfate,
streptomycin sulfate, tobramycin sulfate, miconazole hydrochloride, amanfadine
hydrochloride,
amanfadine sulfate, octopirox, parachlorometa xylenol, nystatin, tolnaftate,
zinc pyrithione and
clotrimazole.
Anti-viral Agents
The compositions of the present invention may further comprise one or more
anti-viral
agents. Suitable anti-viral agents include, but are not limited to, metal
salts (e.g., silver nitrate,
copper sulfate, iron chloride, etc.) and organic acids (e.g., malic acid,
salicylic acid, succinic acid,
benzoic acid, etc.). In particular compositions which contain additional
suitable anti-viral agents
include those described in copending U. S. patent applications Serial Nos.
09/421,084 (Beerse et
al.); 09/421,131 (Biedermann et al.); 09/420,646 (Morgan et al.); and
09/421,179 (Page et al.),
which were each filed on October 19, 1999.
~drocolloids
Hydrocolloids are well known in the art and are helpful in extending the
useful life of the
surfactants. Thus, these would be useful for inclusion particularly in those
embodiments intended
for cleansing the skin, e.g., a showering or bathing experience. Suitable
hydrocolloids include,
but are not limited to, xanthan gum, carboxymethyl cellulose, hydroxyethyl
cellulose,
hydroxylpropyl cellulose, methyl and ethyl cellulose, natural gums, gudras
guar gum, bean gum,
natural starches, deionitized starches (e.g., starch octenyl succinate) and
the like.
18
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
Oil-soluble Polymeric Gellinq Aqents
The compositions of the present invention may optionally comprise one or more
polymeric
materials that are oil-soluble and form a gel with hydrophobic materials (e.g.
oils) that are
contained in the compositions. Such polymers are beneficial for structuring
these materials
resulting in flexible gels with improved stability and shear-resistance.
Particularly suitable are at least partially cross-linked oil-soluble
polymeric materials with
a softening point < 160° C. Suitable materials come from the chemical
groups of PE
(polyethylenes), PVA (polyvinyl alcohols) and derivatives, PVP
(polyvinylpyrrolidones) and
derivatives, PVP/Alkene Copolymers, PVP/VA copolymers, PVM/MA (methyl vinyl
ether/maleic
anhydride) copolymers and their esters and ethers, particularly poly (alkyl
vinyl ether-co-malefic
anhydride) copolymers, ethylene/VA copolymers, styrene/isoprene,
styrene/ethylene/butylene,
styrene/ethylene/propylene, styrene/ethylene/butylene/styrene and
styrene/butadiene
copolymers. Suitable materials are available e.g. from Dupont (ELVAX~ types),
BASF
(LUVISKOL~ types), Shell (KRATON~ polymers) and ISP (PVP, GANTREZ~ and GANEX~
types).
Hydrophilic Gelling Aqent
The compositions of the invention can also contain a hydrophilic gelling agent
at a level
preferably from about 0.01 % to about 10%, more preferably from about 0.02% to
about 2%, and
especially from about 0.02% to about 0.5%. The gelling agent preferably has a
viscosity (1
aqueous solution, 20° C., Brookfield RVT) of at least about 4000 mPas,
more preferably at least
about 10,000 mPas and especially at least 50,000 mPa-s.
Suitable hydrophilic gelling agents can generally be described as water-
soluble or
colloidally water-soluble polymers, and include cellulose ethers (e.g.
hydroxyethyl cellulose,
methyl cellulose, hydroxypropylmethyl cellulose), polyvinylpyrrolidone,
polyvinylalcohol,
polyquaternium-10, guar gum, hydroxypropyl guar gum and xanthan gum.
Among suitable hydrophilic gelling agents are acrylic acid/ethyl acrylate
copolymers and
the carboxyvinyl polymers sold by the B. F. Goodrich Company under the
trademark of Carbopol
resins. These resins consist essentially of a colloidally water-soluble
polyalkenyl polyether
crosslinked polymer of acrylic acid crosslinked with from 0.75% to 2.00% of a
crosslinking agent
such as for example polyallyl sucrose or polyallyl pentaerythritol. Examples
include Carbopol 934,
Carbopol 940, Carbopol 950, Carbopol 980, Carbopol 951 and Carbopol 981.
Carbopol 934 is a
water-soluble polymer of acrylic acid crosslinked with about 1 % of a
polyallyl ether of sucrose
having an average of about 5.8 allyl groups for each sucrose molecule. Also
suitable for use
herein are hydrophobically-modified cross-linked polymers of acrylic acid
having amphipathic
properties available under the Trade Name Carbopol 1382, Carbopol 1342 and
Pemulen TR-1
(CTFA Designation: Acrylates/10-30 Alkyl Acrylate Crosspolymer). A combination
of the
polyalkenyl pofyether cross-finked acrylic acid polymer and the
hydrophobically modified cross-
19
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
linked acrylic acid polymer is also suitable for use herein. Other suitable
gelling agents suitable for
use herein are oleogels such as trihydroxystearin and aluminium magnesium
hydroxy stearate.
The gelling agents herein are particularly valuable for providing excellent
stability characteristics
over both normal and elevated temperatures.
Neutralizing agents suitable for use in neutralizing acidic group containing
hydrophilic
gelling agents herein include sodium hydroxide, potassium hydroxide, ammonium
hydroxide,
monoethanolamine, diethanolamine and triethanolamine.
Surfactants
Surfactants can also be included into the compositions of the present
invention,
particularly when the compositions are useful for cleansing skin. A lathering
surfactant is
preferred for use in such instances. As used herein, "lathering surfactant"
means a surfactant,
which when combined with water and mechanically agitated generates a foam or
lather. Such
surfactants are preferred since increased lather is important to consumers as
an indication of
cleansing effectiveness. In certain personal care embodiments, the surfactants
or combinations
of surfactants are preferably mild. As used herein, "mild" means that the
surfactants as well as to
the articles of the present invention demonstrate skin mildness at least
milder than common bar
soap matrices that typically comprise a combination of natural soap and
synthetic surfactant (e.g.,
Lever 20000 and ZestO). Methods for measuring mildness, or inversely the
irritancy, of
surfactant containing articles, are based on a skin barrier destruction test.
In this test, the milder
the surfactant, the lesser the skin barrier is destroyed. Skin barrier
destruction is measured by the
relative amount of radio-labeled (tritium labeled) water (3H-H20) that passes
from the test
solution through the skin epidermis into the physiological bufFer contained in
the diffusate
chamber. This test is described by T. J. Franz in the J. Invest. Dermatol.,
1975, 64, pp. 190-195;
and in U. S. Patent No. 4,673,525, to Small et al., issued June 16, 1987.
Other testing
methodologies for determining surfactant mildness well known to one skilled in
the art can also be
used.
A wide variety of lathering surfactants are useful herein and include those
selected from
the group consisting of anionic lathering surfactants, nonionic lathering
surfactants, cationic
lathering surfactants, amphoteric lathering surfactants, and mixtures thereof.
Anionic Lathering Surfactants
Nonlimiting examples of anionic lathering surfactants useful herein are
disclosed in
McCutcheon's, Detergents and Emulsifiers, North American edition (1986),
published by Allured
Publishing Corporation; McCutcheon's, Functional Materials, North American
Edition (1992); and
U. S. Patent No. 3,929,678, to Laughlin et al., issued December 30, 1975.
A wide variety of anionic surfactants are potentially useful herein.
Nonlimiting examples
of anionic lathering surfactants include those selected from the group
consisting of alkyl and alkyl
ether sulfates, sulfated monoglycerides, sulfonated olefins, alkyl aryl
sulfonates, primary or
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
secondary alkane sulfonates, alkyl sulfosuccinates, acyl taurates, acyl
isethionates, alkyl
glycerylether sulfonate, sulfonated methyl esters, sulfonated fatty acids,
alkyl phosphates,
ethoxylated alkyl phosphates, acyl glutamates, acyl sarcosinates, alkyl
sulfoacetates, acylated
peptides, alkyl ether carboxylates, acyl lactylates, anionic
fluorosurfactants, and combinations
thereof. Combinations of anionic surfactants can be used effectively in the
present invention.
Specific examples of alkyl sulfates that may be used are sodium, ammonium,
potassium,
magnesium, or TEA salts of lauryl or myristyl sulfate. Examples of alkyl ether
sulfates that may
be used include ammonium, sodium, magnesium, or TEA laureth-3 sulfate.
Another suitable class of anionic surfactants are the sulfated monoglycerides
of the form
R1 CO-O-CH2-C(OH)H-CH2-O-S03M, wherein R1 is a saturated or unsaturated,
branched or
unbranched alkyl group from about 8 to about 24 carbon atoms, and M is a water-
soluble cation
such as ammonium, sodium, potassium, magnesium, triethanolamine,
diethanolamine and
monoethanolamine. An example of a sulfated monoglyceride is sodium
cocomonoglyceride
sulfate.
Other suitable anionic surfactants include olefin sulfonates of the form R1
S03M, wherein
R1 is a mono-olefin having from about 12 to about 24 carbon atoms, and M is a
water-soluble
cation such as ammonium, sodium, potassium, magnesium, triethanolamine,
diethanolamine and
monoethanolamine. An example of a sulfonated olefin is sodium C14/C16 alpha
olefin sulfonate.
Other suitable anionic surfactants are the linear alkylbenzene sulfonates of
the form R1-
C6H4-S03M, wherein R1 is a saturated or unsaturated, branched or unbranched
alkyl group from
about 8 to about 24 carbon atoms, and M is a water-soluble canon such as
ammonium, sodium,
potassium, magnesium, triethanolamine, diethanolamine and monoethanolamine. An
example of
this anionic surfactant is sodium dodecylbenzene sulfonate.
Still other anionic surfactants suitable for the compositions of the present
invention
include the primary or secondary alkane sulfonates of the form R1 SO3M,
wherein R1 is a
saturated or unsaturated, branched or unbranched alkyl chain from about 8 to
about 24 carbon
atoms, and M is a water-soluble cation such as ammonium, sodium, potassium,
magnesium,
triethanolamine, diethanolamine and monoethanolamine. An example of an alkane
sulfonate
useful herein is alkali metal or ammonium C13-C17 paraffin sulfonates.
Still other suitable anionic surfactants are the alkyl sulfosuccinates, which
include
disodium N-octadecylsulfosuccinamate; diammonium lauryl sulfosuccinate;
tetrasodium N-(1,2-
dicarboxyethyl)-N-octadecylsulfosuccinate; diamyl ester of sodium
sulfosuccinic acid; dihexyl
ester of sodium sulfosuccinic acid; and dioctyl esters of sodium sulfosuccinic
acid.
Also useful are taurates that are based on taurine. Examples of taurates
include N
alkyltaurines such as the one prepared by reacting dodecylamine with sodium
isethionate as
detailed in U.S. Patent No. 2,658,072.
21
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
Another class of suitable anionic surfactants is the acyl isethionates.
Nonlimiting
examples of these acyl isethionates include ammonium cocoyl isethionate,
sodium cocoyl
isethionate, sodium lauroyl isethionate, and mixtures thereof.
Still other suitable anionic surfactants are the alkylglyceryl ether
sulfonates of the form
R1-OCH2-C(OH)H-CH2-S03M, wherein R1 is a saturated or unsaturated, branched or
unbranched alkyl group from about 8 to about 24 carbon atoms, and M is a water-
soluble cation
such as ammonium, sodium, potassium, magnesium, triethanolamine,
diethanolamine and
monoethanolamine. One example is sodium cocoglyceryl ether sulfonate.
Other suitable anionic surfactants include:
1. sulfonated fatty acids of the form R1-CH(S04)-COOH and sulfonated methyl
esters of the
from R1-CH(SO4)-CO-O-CH3, where R1 is a saturated or unsaturated, branched or
unbranched
alkyl group from about 8 to about 24 carbon atoms (e.g., alpha sulphonated
coconut fatty acid
and lauryl methyl ester);
2. phosphates such as monoalkyl, dialkyl, and trialkylphosphate salts formed
by the reaction
of phosphorous pentoxide with monohydric branched or unbranched alcohols
having from about
8 to about 24 carbon atoms (e.g., sodium mono or dilaurylphosphate,
ethoxylated monoalkyl
phosphates, etc.);
3. acyl glutamates corresponding to the formula R1 CO-N(COOH)-CH2CH2-C02M
wherein
R1 is a saturated or unsaturated, branched or unbranched alkyl or alkenyl
group of about 8 to
about 24 carbon atoms, and M is a water-soluble cation (e.g., sodium lauroyl
glutamate and
sodium cocoyl glutamate);
4. alkanoyl sarcosinates corresponding to the formula R1 CON(CH3)-CH2CH2-C02M
wherein R1 is a saturated or unsaturated, branched or unbranched alkyl or
alkenyl group of about
10 to about 20 carbon atoms, and M is a water-soluble cation (e.g., sodium
lauroyl sarcosinate,
sodium cocoyl sarcosinate, and ammonium lauroyl sarcosinate);
5. alkyl ether carboxylates corresponding to the formula R1-(OCH2CH2)x-OCH2-
C02M
wherein R1 is a saturated or unsaturated, branched or unbranched alkyl or
alkenyl group of about
8 to about 24 carbon atoms, x is 1 to 10, and M is a water-soluble cation
(e.g., sodium laureth
carboxylate);
6. acyl lactylates corresponding to the formula R1 CO-[O-CH(CH3)-CO]x-C02M
wherein R1
is a saturated or unsaturated, branched or unbranched alkyl or alkenyl group
of about 8 to about
24 carbon atoms, x is 3, and M is a water-soluble cation (e.g., sodium cocoyl
lactylate);
7. ~ carboxylates, nonlimiting examples of which include sodium lauroyl
carboxylate, sodium
cocoyl carboxylate, and ammonium lauroyl carboxylate;
8. anionic flourosurfactants; and
22
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
9. natural soaps derived from the saponification of vegetable and/or animal
fats & oils
exmaples of which include sodium laurate, sodium myristate, palmitate,
stearate, tallowate,
cocoate.
Any counter cation, M, can be used on the anionic surfactant. Preferably, the
counter
cation is selected from the group consisting of sodium, potassium, ammonium,
monoethanolamine, diethanolamine, and triethanolamine.
Nonionic Lathering Surfactants
Nonlimiting examples of nonionic lathering surfactants that may optionally be
included in
the compositions of the present invention are disclosed in McCutcheon's,
Detergents and
Emulsifiers, North American edition (1986), published by allured Publishing
Corporation; and
McCutcheon's, Functional Materials, North American Edition (1992).
Nonionic lathering surfactants useful herein include those selected from the
group
consisting of alkyl glucosides, alkyl polyglucosides, polyhydroxy fatty acid
amides, alkoxylated
fatty acid esters, sucrose esters, amine oxides, and mixtures thereof.
Alkyl glucosides and alkyl polyglucosides are useful herein, and can be
broadly defined
as condensation products of long chain alcohols, e.g., C8-30 alcohols, with
sugars or starches or
sugar or starch polymers, i.e., glycosides or polyglycosides. These compounds
can be
represented by the formula (S)n-O-R wherein S is a sugar moiety such as
glucose, fructose,
mannose, and galactose; n is an integer of from about 1 to about 1000, and R
is a C8-30 alkyl
group. Examples of long chain alcohols from which the alkyl group can be
derived include decyl
alcohol, cetyl alcohol, stearyl alcohol, lauryl alcohol, myristyl alcohol,
oleyl alcohol, and the like.
Preferred examples of these surfactants include those wherein S is a glucose
moiety, R is a
C8-20 alkyl group, and n is an integer of from about 1 to about 9.
Commercially available
examples of these surfactants include decyl polyglucoside (available as APG
325 CS from
Henkel) and lauryl polyglucoside (available as APG 600CS and 625 CS from
Henkel). Also
useful are sucrose ester surfactants such as sucrose cocoate and sucrose
laurate.
Other useful nonionic surfactants include polyhydroxy fatty acid amide
surfactants, more
specific examples of which include glucosamides, corresponding to the
structural formula:
O R1
R2 C -N-Z
wherein: R1 is H, C1-C4 alkyl, 2-hydroxyethyl, 2-hydroxy- propyl, preferably
C1-C4 alkyl, more
preferably methyl or ethyl, most preferably methyl; R2 is C5 C31 alkyl or
alkenyl, preferably
C7 C19 alkyl or alkenyl, more preferably C9 C17 alkyl or alkenyl, most
preferably C11-C15 alkyl
or alkenyl; and Z is a polhydroxyhydrocarbyl moiety having a linear
hydrocarbyl chain with a least
23
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
3 hydroxyls directly connected to the chain, or an alkoxylated derivative
(preferably ethoxylated or
propoxylated) thereof. Z preferably is a sugar moiety selected from the group
consisting of
glucose, fructose, maltose, lactose, galactose, mannose, xylose, and mixtures
thereof. An
especially preferred surfactant corresponding to the above structure is
coconut alkyl N-methyl
glucoside amide (i.e., wherein the R2C0- moiety is derived from coconut oil
fatty acids).
Processes for making compositions containing polyhydroxy fatty acid amides are
disclosed, for
example, in G.B. Patent Specification 809,060, published February 18, 1959, by
Thomas Hedley
& Co., Ltd.; U. S. Patent No. 2,965,576, to E.R. Wilson, issued December 20,
1960; U. S. Patent
No. 2,703,798, to A.M. Schwartz, issued March 8, 1955; and U. S. Patent No.
1,985,424, to
Piggott, issued December 25, 1934.
Other examples of nonionic surfactants include amine oxides. Amine oxides
correspond
to the general formula R1 R2RgN-~O, wherein R1 contains an alkyl, alkenyl or
monohydroxy alkyl
radical of from about 8 to about 18 carbon atoms, from 0 to about 10 ethylene
oxide moieties, and
from 0 to about 1 glyceryl moiety, and R2 and R3 contain from about 1 to about
3 carbon atoms
and from 0 to about 1 hydroxy group, e.g., methyl, ethyl, propyl,
hydroxyethyl, or hydroxypropyl
radicals. The arrow in the formula is a conventional representation of a
semipolar bond.
Examples of amine oxides suitable for use in this invention include dimethyl-
dodecylamine oxide,
oleyldi(2-hydroxyethyl) amine oxide, dimethyloctylamine oxide, dimethyl-
decylamine oxide,
dimethyl-tetradecylamine oxide, 3,6,9-trioxaheptadecyldiethylamine oxide, di(2-
hydroxyethyl)-
tetradecylamine oxide, 2-dodecoxyethyldimethylamine oxide, 3-dodecoxy-2-
hydroxypropyldi(3-
hydroxypropyl)amine oxide, dimethylhexadecylamine oxide.
Nonlimiting examples of preferred nonionic surfactants for use herein are
those selected
form the group consisting of C8-C14 glucose amides, C8-C14 alkyl
polyglucosides, sucrose
cocoate, sucrose laurate, lauramine oxide, cocoamine oxide, and mixtures
thereof.
Cationic Latherinct Surfactants
Cationic lathering surfactants can also be optionally included in the
compositions of the
present invention. Suitable cationic lathering surfactants include, but are
not limited to, fatty
amines, di-fatty quaternary amines, tri-fatty quaternary amines, imidazolinium
quaternary amines,
and combinations thereof. Suitable fatty amines include monalkyl quaternary
amines such as
cetyltrimethylammonium bromide. A suitable quaternary amine is
dialklamidoethyl
hydroxyethylmonium methosulfate.
Amphoteric Lathering Surfactants
The term "amphoteric lathering surfactant," as used herein, is also intended
to
encompass zwitterionic surfactants, which are well known to formulators
skilled in the art as a
subset of amphoteric surfactants.
A wide variety of amphoteric lathering surfactants can be used in the
compositions of the
present invention. Particularly useful are those which are broadly described
as derivatives of
24
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
aliphatic secondary and tertiary amines, preferably wherein the nitrogen is in
a cationic state, in
which the aliphatic radicals can be straight or branched chain and wherein one
of the radicals
contains an ionizable water solubilizing group, e.g., carboxy, sulfonate,
sulfate, phosphate, or
phosphonate.
Nonlimiting examples of amphoteric or zwitterionic surFactants are those
selected from
the group consisting of betaines, sultaines, hydroxysultaines,
alkyliminoacetates,
iminodialkanoates, aminoalkanoates, and mixtures thereof.
Examples of betaines include the higher alkyl betaines, such as coco dimethyl
carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl
alphacarboxyethyl
betaine, cetyl dimethyl carboxymethyl betaine, cetyl dimethyl betaine
(available as Lonzaine
16SP from Lonza Corp.), lauryl bis-(2-hydroxyethyl) carboxymethyl betaine,
oleyl dimethyl
gamma-carboxypropyl betaine, lauryl bis-(2-hydroxypropyl)alpha-carboxyethyl
betaine, coco
dimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, lauryl bis-
(2-hydroxyethyl)
sulfopropyl betaine, amidobetaines and amidosulfobetaines (wherein the
RCONH(CH2)3 radical
is attached to the nitrogen atom of the betaine), oleyl betaine (available as
amphoteric Velvetex
OLB-50 from Henkel), and cocamidopropyl betaine (available as Velvetex BK-35
and BA-35 from
Henkel).
Examples of sultaines and hydroxysultaines include materials such as
cocamidopropyl
hydroxysultaine (available as Mirataine CBS from Rhone-Poulenc).
Preferred for use herein are amphoteric surfactants having the following
structure:
~- I
wherein R1 is unsubstituted, saturated or unsaturated, straight or branched
chain alkyl having
from about 9 to about 22 carbon atoms. Preferred R1 has from about 11 to about
18 carbon
atoms; more preferably from about 12 to about 18 carbon atoms; more preferably
still from about
14 to about 18 carbon atoms; m is an integer from 1 to about 3, more
preferably from about 2 to
about 3, and more preferably about 3; n is either 0 or 1, preferably 1; R2 and
R3 are
independently selected from the group consisting of alkyl having from 1 to
about 3 carbon atoms,
unsubstituted or mono-substituted with hydroxy, preferred R2 and R3 are CH3; X
is selected from
the group consisting of C02, SO3 and S04; R4 is selected from the group
consisting of saturated
or unsaturated, straight or branched chain alkyl, unsubstituted or
monosubstituted with hydroxy,
having from 1 to about 5 carbon atoms. When X is C02, R4 preferably has 1 or 3
carbon atoms,
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
more preferably 1 carbon atom. When X is S03 or S04, R4 preferably has from
about 2 to about
4 carbon atoms, more preferably 3 carbon atoms.
Examples of amphoteric surfactants of the present invention include the
following
compounds:
Cetyl dimethyl betaine (this material also has the CTFA designation cetyl
betaine)
Cocamidopropylbetaine
t~'-~ -l~f ~T<y(~ ~~~g ~f -~ ~1~ (~ ~ ~
wherein R has from about 9 to about 13 carbon atoms
Cocamidopropyl hydroxy sultaine
t~-C-IVf~-Q(~~~~-~~f-C~~ (~~-c~~~ ~Q~~
wherein R has from about 9 to about 13 carbon atoms,
Examples of other useful amphoteric surfactants are alkyliminoacetates, and
iminodialkanoates and aminoalkanoates of the formulas RN[(CH2)mC02M]2 and
95 RNH(CH2)mC02M wherein m is from 1 to 4, R is a Cg-C22 alkyl or alkenyl, and
M is N, alkali
metal, alkaline earth metal ammonium, or alkanolammonium. Also included are
imidazolinium
and ammonium derivatives. Specific examples of suitable amphoteric surfactants
include sodium
3-dodecyl-aminopropionate, sodium 3-dodecylaminopropane sulfonate, N-higher
alkyl aspartic
acids such as those produced according to the teaching of U. S. Patent
2,438,091; and the
products sold under the trade name "Miranol" and described in U. S. Patent
2,528,378. Other
examples of useful amphoterics include amphoteric phosphates, such as
coamidopropyl PG-
dimonium chloride phosphate (commercially available as Monaquat PTC, from Mona
Corp.).
Also useful are amphoacetates such as disodium lauroamphodiacetate, sodium
lauroamphoacetate, and mixtures thereof.
Preferred lathering surfactants are selected from the group consisting of
anionic lathering
surfactants selected from the group consisting of ammonium lauroyl
sarcosinate, sodium
trideceth sulfate, sodium lauroyl sarcosinate, ammonium laureth sulfate,
sodium laureth sulfate,
26
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
ammonium lauryl sulfate, sodium lauryl sulfate, ammonium cocoyl isethionate,
sodium cocoyl
isethionate, sodium lauroyl isethionate, sodium cetyl sulfate, sodium
monolauryl phosphates,
ethoxylated monoalkyl phosphates, sodium cocoglyceryl ether sulfonate, sodium
C9-C22 soap,
and combinations thereof; nonionic lathering surfactants selected from the
group consisting of
lauramine oxide, cocoamine oxide, decyl polyglucose, lauryl polyglucose,
sucrose cocoate, C12-
14 glucosamides, sucrose laurate, and combinations thereof; cationic lathering
surfactants
selected from the group consisting of fatty amines, di-fatty quaternary
amines, tri-fatty quaternary
amines, imidazolinium quaternary amines, and combinations thereof; amphoteric
lathering
surfactants selected from the group consisting of disodium
lauroamphodiacetate, sodium
lauroamphoacetate, cetyl dimethyl betaine, cocoamidopropyl betaine,
cocoamidopropyl hydroxy
sultaine, and combinations thereof.
ASSOCIATED METHODS
Applicant has found that the compositions of the present invention are useful
in a variety
of applications directed to enhancement of proteinaceous substrates like skin,
hair, nails, and
cuticles. The application that is targeted will depend upon the cosmetic
benefit agent that is
attached to the bonding agent. It is expected, however, that a skilled artisan
is capable of
envisioning the appropriate cosmetic benefit agent of those disclosed herein
that are
commensurate with the method of use being disclosed. The methods of use for
the compositions
disclosed and claimed herein include, but are not limited to: 1 ) methods of
increasing the
substantivity of a cosmetic active to skin; 2) methods of moisturizing skin;
3) methods of improving
the natural appearance of skin; 4) methods of applying a color cosmetic to
skin; 5) methods of
deodorizing skin; 6) methods of providing antiperspirant efficacy to skin; 7)
methods of preventing,
retarding, and/or treating wrinkles; 8) methods of providing UV protection to
skin; 9) methods of
preventing, retarding, and/or treating cellulite; 10) methods of preventing,
retarding, and/or
controlling the appearance of oil; and 11 ) methods of modifying the feel and
texture of skin; 12)
methods of providing even skin tone; 13) methods of preventing, retarding,
and/or treating the
appear of spider vessels and varicose veins; 14) methods of masking the
appearance of vellus
hair on skin; 15) methods of concealing blemishes and/or imperfections in
human skin, including
acne, age spots, freckles, moles, scars, under eye circles, birth marks, post-
inflammatory
hyperpigmentation, etc.; and 16) methods of preventing, retarding, and/or
treating malodor of a
mammal. Each of the methods discussed herein involve topical application of
the claimed
compositions on to proteinaceous substrates, particularly skin.
EXAMPLES
The following examples further describe and demonstrate embodiments within the
scope of
the present invention. In the following examples, all ingredients are listed
at an active level. The
examples are given solely for the purpose of illustration and are not to be
construed as limitations
27
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
of the present invention, as many variations thereof are possible without
departing from the spirit
and scope of the invention.
For each of the diazonium salt bonding agents listed below, m = 1 to 100, n =
1 to 100, y =
1 to 20, and z = 2 to 500.
Example 1
Antioxidant-modified bonding agent- Modified ascorbate
O
_C~+
Example 2
Antioxidant-modified bonding agent- Modified gallate
N=NCt
O
H i
H
OH
Example 3
N+ NCI'
2$
Colorant-modified bonding agent - Modified FD&C Yellow 6
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
Example 4
Colorant-modified bonding agent-Modified D&C Red 36
NOZ
CI
10
N
N+=NCI'
O i
n
Example 5
Colorant-modified bonding agent - Modified D&C Green 8
i03Na
303Na
Example 6
Humectant-modified bonding agent-Modified glycerol
H N'-NCt
H
Example 7
Humectant-modified bonding agent- Modified PEG
29
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
'GIN= N
O
O
m
N=NCI'
Example 8
Silicone-modified bonding agent
N+=NCE
In
Si- Si-
Example 9
Silicone-modified bonding agent
N-NCE
p-S' O-S' O-Si-O n
m
+N=NCE
Example 10
Sunscreen-modified bonding agent-Modified benzophenone-3
30
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
O N+ NCI-
i
n
OCH3
Exam~~le 11
Sunscreen-modified bonding agent - Modified octyl methoxycinnamate
0
O 3
n
-CIN=+N / H3C0
Example 12
A lipstick product is prepared by mixing the following ingredients as detailed
below.
Ingredient Wt
Polybutene 4.536
Lanolin Oil 18.342
Octoxyglyceryl Behenate 18.342
Stearyl heptanoate 8.856
Jojoba oil 8.856
Castor oil 21.78
Butylated hydroxytoluene 0.054
Butylated hydroxyanisole 0.054
Microcrystalline Wax 6.84
Polyethylene 500 6.84
Modified D&C Red 36 (from Example4.5
2)
(Amphiphlic lipid phase)
Lecithin 0.475
Cholesterol 0.475
dicetyl phosphate 0.05
31
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
Recrystallize modified D&C Red 36 using the single solvent method. Mill
modified D&C Red
36 with Castor oil until desired Particle size is reached. Mixing of the
different compounds is
performed at a temperature between 100-120 C with stirring until fully
homogenous. Heat
amphiphilic lipid phase to 100 C under nitrogen, add phases together, mill
until uniform, mold,
and cool.
Example 13
A foundation compact product is prepared by mixing the following ingredients
as indicated below.
Phase Silicone Elastomer Compact Wt
A Ti02 silicone treated 5.25
Hydrophobic Yellow Iron Oxide Slurry
A (55% Pigment,
16.15% Cyclomethicone, 28.85% Dimethicone.80
Copolyol)
Hydrophobic Red Iron Oxide Slurry
A (70% pigment, 0.31
10.7%cyclomethicone, 19.3% Dimethicone
Copolyol)
Hydrophobic Black Iron Oxide Slurry
A (65% pigment, 0.12
13.2% cyclomethicone, 21.8% Dimethicone
Copolyol)
A Hydrophobic Talc 2.36
A Ti02 -MT100T (micronized) 0.16
A DC245 (cyclomethicone) 74.96
A DC5225C (dimethicone copolyol - 0.31
10% active)
B Silicone Elastomer 2.40
B propylparaben (preservative) 0.00
B Modified Glycerol (from Example 7.08
4)
C Ozokerite Wax 6.25
The pigment slurries are created by combining the pigment, wetting agent
(cyclomethicone),
and dispersant (copolyol) and milling to the desired particle size.
Ingredients in phase A are
added together and high shear milled until the desired particle size. Phase B
ingredients are
added to phase A ingredients and mixed until uniform. The mixture of phase A
&B is heated
while mixing to 85-90 C. Phase C is added and mixed until completely melted
and the
mixture is uniform. The mixture is then poured into a mold.
Example 14
A Ii e1 roduct is re ared b combinin the followin in redients as detailed
below.
Ingredient Wt
Silicone elastomer 4.0
32
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
cyclomethicone 83.0
Dimethicone Fluid 4.5
Modified D&C Green 8 (from Example6
3)
Modified FD&C Yellow 6 (from Example2.5
1 )
All Ingredients are mixed together using low to medium shear.
Example 15
A lip balm product is prepared by combining the following ingredients as
detailed below.
Phase Ingredient Wt
A Petrolatum 10.0
Modified Glycerol
A (from 10.0
Example 4)
A Silicone elastomer 3.4
A cyclomethicone 64.3
A Dimethicone copolyol5.0
A Preservative 0.3
B Ozokerite wax 7.0
Ingredients in phase A are added together and mixed using low shear until
uniform. Phase A
is heated to 85-90 C while mixing. Phase B is added and mixed until uniform.
This mixture is
then poured into a mold.
Example 16
A moisturizing lotion is prepared by mixing the ingredients as detailed below.
1n_ reg-dient Wt
Main Water Phase
USP Water 63.77435
Disodium EDTA 0.100
Arlatone 2121 1.00
Part D - Particulate
Premix
(D) USP Water 5.000
(D) Glycerine 6.930
(D) Kobo Titanium 0.544
Dioxide
Part A- Neutralization
Premix
(A) USP Water 3.013
(A) Sodium Hydroxide 0.0125
33
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
Part B - Niacinamide
Premix
(B) USP Water 5.000
(B) Panthenol 0.500
Modified Ascorbate2.000
(B) (from
Example 8)
(B) FD&C Yellow No. 0.00115
5
(B) FD&C Red No. 0.00050
40
(C) Sefa Cottonate 0.670
(C) Isopropyllsostearate1.330
(C) Tocopherol Acetate0.500
(C) Permethyl 101 3.000
A
(C) Cetyl Alcohol 0.720
CO-1695
(C) Adol 62 0.480
(C) Nipigin A 0.200
(C) Ueno Propylparaben0.100
NF
(C) Emersol 132 0.100
(C) Myrj 59 0.100
Part E
(E) Sepigel 2.500
Q2-1403 2.000
Benzyl Alcohol 0.250
Fiery 5 0.175
In an appropriate container, prepare the Neutralization Premix. Add part A
ingredients to
container and mix with a stir bar until homogenous. In an appropriate
container prepare Part D
(Particulate Premix). Mix by mixer until homogenous. In an appropriate
container, prepare the
modified ascorbate premix. Add Part B ingredients into container, except FD&C
Yellow/Red.
Heat to no higher than 40 °C while mixing until modified ascorbate is
dissolved. Add FD&C
Yellow/Red. Mix until dissolved. Prepare the Oil Phase. Add part C ingredients
to oil phase
except Permethyl 101A and begin heating to 70-80 °C while mixing
Maintain Temperature once
heated. Prepare the water phase. Add USP water to appropriate pyrex beaker,
and begin
heating to 70-80 C while mixing with a prop blade at 250-500 rpm. When water
phase is between
70-80 °C add Disodium EDTA and Arlatone 2121 to beaker and allow to
dissolve. Mix at least 5
minutes. When Oil & Water phases are between 70-80 °C begin to mill
water phase. Slowly add
oil phase to water phase while milling. Mill for 2-3 min. Add Particulate
premix(part D) slowly, by
34
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
hand pouring Add neutralization premix (part A) slowly. Cool batch to 60
°C and add sepigel.
Switch to U-blade once formula looks smooth. Cool batch to 50 °C, then
add modified ascorbate
premix, Benzyl alcohol and Q2-1402. Cool batch to 40 °C with periodic
spatula mixing to insure
homogeneity. When temperature reaches 40 °C, add fragrance. Mill for 2-
3 minutes.
Example 17
A solid antiperspirant stick of the present invention is prepared as follows:
Inctredient Wt
Modified Gallate (from Example 8.0
9)
Stearyl Alcohol 10.0
Hydrogenated Castor Oil-mp 86 4.0
degrees C.
Aluminum Chlorohydroxide 40.0
Isopar "V"' 37.0
Fragrance 1.0
'(Isopar "V" Avg. Mol. Wt. 197 B.P. Range, 255-301 degrees C.)
In a suitable vessel, neat, chemically synthesized modified ascorbate is
dissolved using
an appropriate solvent. The modified asdcorbate is then recrystallized by
sublimation method.
Next, the recrystallized modified ascorbate is milled to the appropriate
particle size.
In separate vessel containing a heat source, the isoparaffin liquids, the
water-insoluble
liquid emollients, the surface active agent, and the water-insoluble waxes are
heated to a
temperature sufficient to form a solution of these materials. Next, the
aluminum chlorohydroxide
is added with gentle agitation, followed by the recrystallized modified
ascorbate and remaining
ingredients. The solution is mixed until a homogenous suspension is formed.
The suspension is
cooled to a temperature above the solidification point and is then poured into
suitable containers.
An antiperspirant composition, comprised as above, is applied to the underarm
area of a human
subject, and reduces the perspiration in the applied area.
Example 18
A long wearing eye shadow is prepared including the following ingredients that
are mixed
as detailed below.
Ingiredient Wt
Pearl Mica CF ~ ~~~ 4.41
Glycerol Ester of Tall Oil Rosin 3.00
GE SFE 839 Cross-linked Siloxane Elastomer 44.6
gel'
Polyethylene AC-617A 5.46
Beeswax White, Flakes 3.00
Propylparaben, NF 0.10
Tenox BHA 0.20
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
Bentone 38 CF or Type 5.40
Propylene Carbonate 1.00
Phenoxyethanol 0.80
Modified D&C Green 8 (from Example 3) 0.18
Talc 2755 3.00
Magnesium Carbonate 309 2.00
Glyceryl Tribehenate ' 2.00
Paraffin Wax 1.50
Modified Silicone (from one of Examples 10 1.30
or 11 )
Vanillin 0.01
Lecithin, Liquid 0.54
Aluminum Starch Octenyl Succinate 5.00
Pigment 16..5
' 5% Dimethicone/vinyl dimethicone cross-polymer in cyclomethicone.
Example 19
A long wearing sunscreen product is prepared as detailed below.
Ingredient Wt%
Water QS100
Glycerine 3.00
Disodium EDTA 0.10
Methyl Paraben 0.25
Sepigel 305 2.00
Octyl Salicylate 5.00
Modified Benzophenone-3 (from 2.00
Example 6)
Modified octyl methoxycinnamate1.50
(from
Example 7)
Isohexadecane 2.00
Steareth-21 0.80
Stearetch-2 0.10
Cetyl alcohol 0.80
Stearyl Alcohol 0.80
Behenyl Alcohol 0.80
Propyl Paraben 0.15
Prepare a water phase by combining the water, glycerin, disodium EDTA, methyl
paraben in an
appropriate vessel with mixing and heating to approximately 75 °C.
Prepare the oil phase by
combining the modified benzophenone-3, octyl methoxycinnamate, isohexadecane,
cetyl alcohol,
36
CA 02448227 2003-11-24
WO 02/072056 PCT/US02/06567
stearyl alcohol, propyl paraben , octyl salicyclate, steareth-21, steareth-2,
and behenyl alcohol
into a separate vessel with mixing and heating to approximately 75 °C.
Mix the oil phase into the
water phase with shearing to form an emulsion. Cool the emulsion to 60
°C with shearing and
add Sepigel 305. Slowly stir the emulsion and cool to approximately 30
°C, and package as
desired.
Example 20
A long wearing sunscreen product is made as detailed below.
Ingredient Wt%
Water QS100
Glycerine 2.00
Disodium EDTA 0.10
Methy Paraban 0.25
Sepigel 305 2.50
2-Phenyl-Benzimidazole 5-Sulphonic1.00
Acid
Triethanolamine 0.50
Octyl Salicylate 3.00
Modified Benzophenone-3 (from 2.00
example 6)
2-ethylhexyl-p-methoxycinnamate 1.33
Isohexadecane 2.00
Cetyl alcohol 0.70
Stearyl Alcohol 0.70
Propyl Paraben 0.15
Modified PEG-100 (from Example 0.10
5)
Prepare a water phase by combining the water, glycerin, disodium EDTA, methyl
paraben in
an appropriate vessel with mixing and heating to approximately 75 °C.
Prepare the oil phase by
combining the modified benzophenone-3, 2-ethylhexyl-p-methoxycinnamate,
isohexadecane,
cetyl alcohol, stearyl alcohol, propyl paraben, octyl salicyclate, and
modified PEG-100 into a
separate vessel with mixing and heating to approximately 75 °C. Mix the
oil phase into the water
phase with shearing to form an emulsion. Cool the emulsion to 60 °C
with shearing and add
Sepigel 305, 2-phenyl-benzimidazole-5-sulphonic acid, and triethanolamine.
Slowly stir the
emulsion and cool to approximately 30 °C, and package as desired.
37
